577874 A7 B7 五、發明説明（1 ) 發明背景 1 .發明領域 本發明係關於一種經由於液相氧化二烷基芳族醛及其氧 化物衍生物生產偏苯三酸之方法，及由偏苯三酸生產高品 質偏苯三酸酐之方法。 2 .先前技術之說明 習知芳族多羧酸係經由氧化多烷基苯生產，已知偏苯三 酸得自1，2,4-三甲基苯，均苯三酸得自1,3, 5-三甲基苯， 均苯四酸得自1,2,4,5-四甲基苯及偏苯四酸得自1,2,3,5 -四甲基苯。例如，JP-A-6- 1 6655揭示經由於液相氧化1，2 , 4-三甲基苯生產偏苯三酸之方法，其中氧化係於鈽、鈷及 錳存在下進行，及選擇性於銷及溴催化劑共同存在下進行 ，鈽及溴許可藉批次法於第二氧化步驟反應。但因前逑催 化劑系統複雜，又因反應方法複雜，故難K回收及循環利 用催化劑。 經漪部中央標率局貝工消費合作社印^ (請先閱讀背面之注意事項再填寫本頁) 烷基苯氧化成對應芳族多羧酸時，烷基苯依據取代甲基 位置而定彼此反應性不同。由1,2 ,4-三甲基苯或1,2,4,5-四甲基苯生成之偏苯三酸或均苯四酸之結構為其中一個羧 酸位於另一個羧酸之鄰位，故重金屬催化劑之活性下降， 氧化所得產率比較具有此種結構之多甲基苯降低。因此做 出多種提議改良催化劑系統。氧化所得產率改良，但因催 化劑糸統複雜，故難Μ回收及再利用催化麵。 它方面，已知芳族醛係經由轉化芳族烴成為甲醜基生成 ，用做生產芳族多狻酸之原料。例如，JP-B-58-2222揭示 本紙張尺度適用中國國家標準（^^)八4规枱（210/ 297公漦） -A - 577874 A7 B7 五、發明説明（2 ) 一種方法其中芳族醛於水溶劑氧化而連續生產芳族多羧酸 。此種方法因溴濃度高故需由銷製成的特殊反應器材料。 又，JP-A-57-38745揭示一種方法其中多烷基芳族醛於 鈷、錳及溴存在下與乙酸溶劑氧化生產芳族多羧酸。 塑膠業界使用偏苯三酸做為合成樹脂或增塑劑之中間物 。許多例中，偏苯三酸藉脫水轉成偏苯三酸酐，特別用做 生產聚酯之中間物。因此強烈需要供給廉價偏苯三酸。 發明人研究根據前述JP-A-57-38745之方法經由於鈷、 錳及溴存在下於乙酸溶劑氧化二烷基芳族醛生產偏苯三酸 而發現下列。由於晶體之金屬含量大，故難Μ回收及循環 催化劑，鑑於產率也需額外改良。 本發明之第一目的係提供一種生產偏苯三酸之方法，其 無需任何特殊反應器材料供連缋氧化二烷基芳族醛及/或 其氧化物衍生物，其許可循環利用催化劑即獲得高產率。 使用類似JP-A-57-38 745之鈷、錳及溴組成之催化劑系 統之方法時，需要改良反應速率及產率。 經漓部中央標率局貝工消費合作社印^ (請先閱讀背面之注意事項再填寫本頁) 本發明之第二目的係提供一種於開發用來替代鈷、錳及 溴之催化劑系統之高活性催化劑存在下，由二烷基芳族醛 及/或其氧化物衍生物做為原料連練及優異生產偏苯三酸 之方法。 偏苯三酸為芳族三元酸，主要做為高級增塑劑或耐熱塑 膠原料。增塑劑或塑膠需要色钐較淺之高純度偏苯三酸酐 倣為原料。 如JP-Β-58-2222及JP-A-6 1 -280448所述，偏苯三酸酐係 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210Χ 297公f ) -5 - 577874 經濟部中央標隼局貝工消費合作社印製 A7 B7五、發明説明（3 ) 由粗偏苯三酸獲得，後者係經由於溴離子存在下或於溴離 子及重金屬離子做為催化劑存在下，使用分子氧氧化1,2, 4-三甲基苯，二甲基苯甲醛或其氧化物中間物獲得。 偏苯三酸酐係經由如Ullman參考文獻（"Encyclopedia of Industrial Chemistry"，4th ed. v ο K 9* page 150) 於220至230 1C加熱脫水出偏苯三酸及於減壓條件下蒸餾所 得偏苯三酸酐生產。 但藉前述方法生產之偏苯三酸酐之色度及純度不一定滿 意，近年來需要供給具有更高品質之偏苯三酸酐做為高级 增塑及/或耐熱塑膠原料。 JP-B-47-3 5 42 1揭示一種方法其中偏苯三酸係使用硼酸 處理。又，為了改良此種方法，日本PCT公告案第4-50 1 27 1 號揭示一種方法其中至少0 . 1 %重量比硼添加至偏苯三酸酐 ，混合物經加熱處理及處理妥之偏苯三酸酐經蒸餾供改良 其色度。 但藉前述方法生產之偏苯三酸酐之色度及純度無需滿意 ，近年來希望提供具有遶更高品質之偏苯三酸酐做為高级 增塑劑或耐熱塑膠原料。 又，當做為原料之1,2, 4-三甲基苯或二甲基苯甲醛含有 無法藉氧化轉成偏苯三酸之雜質時，所得偏苯三酸酐之色 度及純度於某些例中劣化，因此希望開發一種生產不含因 原料造成影響之偏苯三酸酐之方法。 本發明之第三目的係提供一種於產業上由具有低純度且 含有色物質經由氧化1，2 , 4-三甲基苯或二甲基苯甲醛所得 (請先閱讀背面之注意事項再填寫本頁) 一裝· 、1Τ έ 本紙張尺度適用中國國家標準（CNS ) Λ4規枱（21〇Χ 297公梦） 一 6 一 577874 A7 B7 五、發明説明（4 ) 粗製偏苯三酸優異地生產高品質偏苯三酸酐之方法。 丨發明概逑 發明人致力於研究克服前述有關生產偏苯三酸之方法， 結果發琨下列。二烷基醛及其氧化物衍生物氧化過程中， 溶劑之水含量調整至特定範圍，因此晶體所含金鼷濃度顯 著降低，故催化劑可循環利用，偏苯三酸之產率也改良。 基於前述發現，獲得第一發明。 換言之，第一發明提供一種生產偏苯三酸之方法，其包 含於含重金鼷及溴之催化劑存在下，使用含氧氣體於具有 水含量5至70¾重量比之低碳脂族羧酸溶劑於180至240 1氧 化二烷基芳族醛及/或其氧化物衍生物。 又，發明人發現锆-錳-溴催化劑，鈽-錳-溴催化劑及锆 -飾-錳-溴催化劑用於二烷基芳族醛及/或其氧化物衍生物 之氧化具有比鈷-錳催化劑更高活性因而獲得第二發明。 經滴部中央標準局貝工消費合作社印製 (讀先閱讀背面之注意事項再填寫本頁) 換言之，第二發明係有關一種生產偏苯三酸之方法，其 包含於含锆及/或鈽之溴-錳催化劑系統存在下於180 1C至 2 40 °C之溫度於含低碳脂族羧酸溶劑氧化二烷基芳族醛及/ 或其氧化物衍生物。 又，發明人積極研究克服偏苯三酸酐之色度性質不良問 題，结果發現下列。於改良偏苯三酸酐色度之日本PCT公 告案第4-50 1 27 1號之方法中，添加之硼氧化物於蒸餾過程 濃縮於蒸餾柱底，底液體變成具有高沸點，底餾分溫度升 高及殘餘物黏度增高。結果於產業上難Μ蒸餾。 相反地，偏苯三酸酐經蒸餾及分離伴Κ循環蒸餾柱底液 本紙張尺度適用中國國家標準（CNS ) Λ4規枱（210Χ 297公# ) ^ 577874 經滴部中央標準局員工消費合作社印製 五、發明説明（5 液之，偏第 酐烷 酸產熱 量 ο 曰皿❾苯 熱長或偏明 底酐理之得 酸二 W 三理加 其90Mr偏 加理比度發 柱酸處度獲 三 ，¾ 苯處至 ，至 CX, 由處量純四 餾三熱純， 苯苯 Μ 偏熱體 硼5003ί中 經熱重低第 蒸苯加低果 偏代 δ 水加液 化為25h 酐 與加3¾有得 止偏下具結 產取¾脫將底 氧物於 W 酸 酸下至具獲 防與在由。 生基一？ 熱後之 加合下 π 三。三壓量地， 而酸存地酐 酸族 加然柱 添混壓 W 苯下苯減含異果 因三硼異酸 三脂">由，餾 佳酐減IL偏 Μ 偏於酸優結 , 苯化優三 苯4~(i經物蒸 較酸之 Μ 或或物三及。 器偏氧定苯 偏2,17或合於 ，三下 f 比酸合苯定酐 容或之穩偏 由1,^酸混份 中苯以1¾量三混偏穩酸 理酸量而之 種化Hit三之部 理偏或ii重苯酐低可三 處三小因質 一氧 f 苯酐環 處與耳 u3¾偏酸降此苯 熱苯最，品 供由 偏酸循 熱酸托pi或為。三 俾因偏 即偏需物高 提經 ^ 理三績 加三οοίΰ酸佳述苯物，質 亦粗所產有 明係 ί 處苯連 硼苯$2u 三 較下偏化餾品 ， ， 於應具 發酸纟熱偏及 用偏 苯量現得氧蒸高 驟又下反產 三三 Μ 加與， 使或 i 偏含發所硼行產 步。壓除生 第苯 Ϊ 下酸柱 之酸 之量人酸加進生 理點減去料 ，餳及壓三餾。明三 U β 柱總明三添後料 處沸於餾原。之，醛減苯蒸驟發苯0*5 餾於發苯未然原 熱高物蒸酸明言法甲於偏進步三偏力行蒸基，偏而，酸 至較合後三發換方苯硼得引理第於 m 進進酸又水間下三 體之混然苯三 之基化所物處 基PP度引三 脫時M苯 ----2--^--i --：--; (請先閱讀背面之注意事項再填寫本買) •丨訂------ 1 j - —I— HJ. 本紙張尺度適用中國國家標準（CNS ) Λ4規枱（210X 297公梦 577874 A7 B7 五、發明説明（6 ) 換言之，第四發明提供一種由經由氧化1，2, 4-脂族基取 代苯，二烷基苯甲醛及/或其氧化物中間物所得粗偏苯三 酸生產偏苯三酸酐之方法，該方法包含加熱處理偏苯三酸 或偏苯三酸與經由加熱脫水偏苯三酸所得偏苯三酸酐混合 物至偏苯三酸基於偏苯三酸與偏苯三酸總量之含量為3¾重 量比或Μ下，及將加熱處理產物引進蒸餾柱。較佳於加熱 處理條件下，減壓為200托耳或Μ下，溫度至少250 °C及處 理時間至少3 0分鐘。 圖式之簡單說明 圖1顯示藉第三發明提供之偏苯三酸酐製法之流程圖範 例。 發明之詳细說明 用於第一及第二發明氧化原料之二烷基芳族醛包括2 , 4-二甲基苯甲醛，2,5-二甲基苯甲醛及3, 4-二甲基苯甲醛。 其氧化物衍生物包括2, 4-二甲基苯甲酸，2, 5-二甲基苯甲 酸，3,4-二甲基苯甲酸，甲醯基甲基苯甲酸及甲基酞酸。 經滴部中央標準局員工消費合作社印製 (讀先閱讀背而之注意事項再填寫本頁) 前述氧化中用做溶劑之低碳脂族羧酸為含1至5個碳原子 之脂族一羧酸，其可選自甲酸、乙酸、丙酸、丁酸或其混 合物。Μ乙酸及丙酸為佳，及Μ乙酸為特佳。 溶劑之水含量為5至70¾重量比，較佳10至60¾重量比。 當水含量低於前述下限時，易生成偏苯三酸與重金鼷鹽， 因而催化劑活性下降。當水含量高於前述上限時，反應速 率降低，故產率低。 溶劑對二烷基芳族醛及其氧化物衍生物之數量通常為1 本紙張尺度適用中國國家標準（CNS)Λ4規格（ 210X 297公#) 9 經濟部中央標準局員工消費合作社印製 577874 A7 B7 五、發明説明（7 ) 至20倍，較佳為3至10倍。 第一發明之氧化物使用重金鼷做為催化劑，單獨使用錳 或錳與鈷做為催化劑。第二發明之氧化使用_及/或鈽之 基於溴-錳之催化劑做為催化_。 此等錳、鈷、_及鈽化合物包括有機鹽類，鹵化物及碳 酸鹽類。特別，較佳呈乙酸鹽或溴化物形式使用。 用做氧化催化劑之溴化合物並無特殊限制，只要不溶解 反應系統及產生溴離子即可。溴化合物包括無機溴如溴化 氫，溴化鈉及溴化鈷，及有機溴如四溴乙烷。特別，以溴 化氫，溴化鈷及溴化錳為佳。 根據第二發明，锆和鈽添加至錳-溴系統催化劑。本例 中，催化劑活性增高，反應速率大為改良。特佳添加锆及 鈽0 重金屬於溶劑之濃度為0.03至2¾重量比，較佳0,05至U 重量比◊當催化劑濃度低於前逑下限時，未進行反應。當 催化劑濃度超過前述上限時，催化劑對反應造成不良影響 。錳通常用倣重金靨，而鈷用做部份重金靥。 當锆及鈽添加至錳時，重金屬組成比較佳如下。基於重 金屬總量，锆含量為1至10¾重量比，鈽含量為1至20¾重量 比，及錳含量為70至98¾重量比。 溶劑之溴濃度為0.05至2¾重量比，較佳0. 1至1¾重量比 。當溴濃度低於前述下限時，無法進行反應。當溴濃度高 於前述上限時，出現嚴重腐蝕。重金屬催化劑對溴陰離子 之原子比為0 . 5至1 0，較佳0 . 8至匕_____ 本紙張尺度適用中國國家標準（CNS ) Λ4%枱（210X297々$ ) 一 10 - (請先閱讀背面之注意事項再填寫本頁)577874 A7 B7 V. Description of the invention (1) Background of the invention 1. Field of the invention The present invention relates to a method for producing trimellitic acid by liquid-phase oxidation of a dialkyl aromatic aldehyde and its oxide derivative, and from trimellitic acid Triacid method for producing high quality trimellitic anhydride. 2. Description of the prior art. Conventional aromatic polycarboxylic acids are produced by oxidizing polyalkylbenzenes. Trimellitic acid is known to be obtained from 1,2,4-trimethylbenzene and trimesic acid is obtained from 1,3,5. -Trimethylbenzene, pyromellitic acid from 1,2,4,5-tetramethylbenzene and trimellitic acid from 1,2,3,5-tetramethylbenzene. For example, JP-A-6- 1 6655 discloses a method for producing trimellitic acid by liquid-phase oxidation of 1,2,4-trimethylbenzene, wherein the oxidation is performed in the presence of thallium, cobalt, and manganese, and the selectivity is It is carried out in the presence of a pin and a bromine catalyst, and the thallium and bromine may be reacted in a second oxidation step by a batch method. However, it is difficult to recover and recycle the catalyst due to the complexity of the former catalyst system and the complicated reaction method. Printed by the Central Standards Bureau of the Ministry of Economics and Labor of the Bayer Consumer Cooperative ^ (Please read the notes on the back before filling out this page) When alkylbenzenes are oxidized to the corresponding aromatic polycarboxylic acids, the alkylbenzenes are based on the position of the substituted methyl groups. Reactivity is different. The structure of trimellitic acid or pyromellitic acid produced from 1,2,4-trimethylbenzene or 1,2,4,5-tetramethylbenzene is that one carboxylic acid is located in the ortho position of the other carboxylic acid Therefore, the activity of the heavy metal catalyst is reduced, and the yield of oxidation is lower than that of polymethylbenzene having such a structure. Therefore, various proposals have been made to improve the catalyst system. The yield from the oxidation is improved, but because the catalyst system is complicated, it is difficult to recover and reuse the catalytic surface. In this regard, it is known that aromatic aldehydes are converted to methyl radicals by conversion of aromatic hydrocarbons, and are used as raw materials for the production of aromatic polycarboxylic acids. For example, JP-B-58-2222 reveals that this paper size is applicable to the Chinese National Standard (^^) 8-4 gauge (210/297 gong) -A-577874 A7 B7 V. Description of the invention (2) A method in which aromatic The aldehyde is oxidized in an aqueous solvent to continuously produce aromatic polycarboxylic acids. This method requires special reactor materials made of pins due to the high bromine concentration. Also, JP-A-57-38745 discloses a method in which a polyalkylaromatic aldehyde is oxidized with an acetic acid solvent in the presence of cobalt, manganese, and bromine to produce an aromatic polycarboxylic acid. The plastics industry uses trimellitic acid as an intermediate in synthetic resins or plasticizers. In many cases, trimellitic acid is converted to trimellitic anhydride by dehydration, and it is especially used as an intermediate for the production of polyester. Therefore, there is a strong need to supply inexpensive trimellitic acid. The inventors studied the production of trimellitic acid by oxidizing a dialkyl aromatic aldehyde in an acetic acid solvent in the presence of cobalt, manganese, and bromine in accordance with the aforementioned method of JP-A-57-38745, and found the following. Due to the large metal content of the crystals, it is difficult to recover and recycle the catalyst, and in view of the yield, additional improvements are needed. A first object of the present invention is to provide a method for producing trimellitic acid, which does not require any special reactor materials for the oxidation of dialkyl aromatic aldehydes and / or its oxide derivatives, and is obtained by using a recycle catalyst. High yield. When a method similar to a catalyst system consisting of cobalt, manganese and bromine of JP-A-57-38 745 is used, it is necessary to improve the reaction rate and yield. Printed by the Central Laboratories of the Ministry of Standards and Industry of the People's Republic of China. (Please read the notes on the back before filling out this page.) The second purpose of the present invention is to provide a catalyst system developed to replace cobalt, manganese and bromine. A method for continuous training and excellent production of trimellitic acid by using a dialkyl aromatic aldehyde and / or an oxide derivative thereof as a raw material in the presence of an active catalyst. Trimellitic acid is an aromatic tribasic acid, which is mainly used as a high-grade plasticizer or a heat-resistant plastic raw material. Plasticizers or plastics require light-colored, high-purity trimellitic anhydride as a raw material. As described in JP-B-58-2222 and JP-A-6 1-280448, trimellitic anhydride is a paper standard that conforms to the Chinese National Standard (CNS) Λ4 specification (210 × 297 male f) -5-577874 Central Bureau of Standards, Ministry of Economic Affairs Printed by Shelley Consumer Cooperative A7 B7 V. Description of the invention (3) Obtained from crude trimellitic acid, which is oxidized with molecular oxygen in the presence of bromide ions or in the presence of bromide ions and heavy metal ions 1, Obtained from 2, 4-trimethylbenzene, dimethylbenzaldehyde or its oxide intermediate. Trimellitic anhydride is produced by heating and dehydrating trimellitic acid at 220 to 230 1C, such as Ullman reference (" Encyclopedia of Industrial Chemistry ", 4th ed. V ο K 9 * page 150), and distillation under reduced pressure. However, the color and purity of trimellitic anhydride produced by the aforementioned method are not necessarily satisfactory. In recent years, it has been necessary to supply trimellitic anhydride with higher quality as a high-grade plasticized and / or heat-resistant plastic raw material. JP-B-47-3 5 42 1 discloses a method in which trimellitic acid is treated with boric acid. In addition, in order to improve this method, Japanese PCT Publication No. 4-50 1 27 1 discloses a method in which at least 0.1% by weight of boron is added to trimellitic anhydride, and the mixture is heat-treated and the processed trimellitic anhydride is distilled for improvement. Chroma. However, the color and purity of trimellitic anhydride produced by the aforementioned method need not be satisfactory. In recent years, it is hoped to provide trimellitic anhydride with higher quality as an advanced plasticizer or heat-resistant plastic raw material. In addition, when 1,2,4-trimethylbenzene or dimethylbenzaldehyde used as a raw material contains impurities that cannot be converted into trimellitic acid by oxidation, the color and purity of the obtained trimellitic anhydride are deteriorated in some cases. It is therefore desirable to develop a method for producing trimellitic anhydride that is free from the effects of raw materials. The third object of the present invention is to provide an industrially obtained low-purity and color-containing substance obtained by oxidizing 1,2,4-trimethylbenzene or dimethylbenzaldehyde (please read the precautions on the back before filling in this Page) 1 pack, 1 Τ This paper size is applicable to Chinese National Standards (CNS) Λ4 gauge (21〇 × 297 public dream) 6 6 577874 A7 B7 V. Description of the invention (4) Crude trimellitic acid is excellently produced Method for high quality trimellitic anhydride.丨 Summary of the invention The inventors have devoted themselves to studying the method for overcoming the aforementioned production of trimellitic acid, and the results are as follows. During the oxidation of dialkylaldehyde and its oxide derivatives, the water content of the solvent is adjusted to a specific range, so the concentration of gold tincture in the crystal is significantly reduced, so the catalyst can be recycled and the yield of trimellitic acid is also improved. Based on the foregoing findings, a first invention was obtained. In other words, the first invention provides a method for producing trimellitic acid, which comprises using an oxygen-containing gas in a low-carbon aliphatic carboxylic acid solvent having a water content of 5 to 70 ¾ by weight in the presence of a catalyst containing heavy gold tincture and bromine. 180 to 240 1 Dialkyl aromatic aldehydes and / or oxide derivatives thereof. In addition, the inventors have found that the zirconium-manganese-bromine catalyst, the hafnium-manganese-bromine catalyst and the zirconium-decorated-manganese-bromine catalyst are used for the oxidation of dialkyl aromatic aldehydes and / or oxide derivatives thereof to have a higher cobalt-manganese oxidation rate. The catalyst was more active and thus the second invention was obtained. Printed by Dibei Central Bureau of Standards, Shellfish Consumer Cooperative (read the precautions on the back before filling this page). In other words, the second invention is a method for producing trimellitic acid, which contains zirconium and / or hafnium The presence of a bromine-manganese catalyst system oxidizes dialkyl aromatic aldehydes and / or its oxide derivatives at a temperature of 180 1C to 2 40 ° C in a solvent containing a low-carbon aliphatic carboxylic acid. In addition, the inventors actively studied to overcome the problem of poor color properties of trimellitic anhydride, and found the following. In the method of Japanese PCT Publication No. 4-50 1 27 1 for improving the color of trimellitic anhydride, the added boron oxide is concentrated on the bottom of the distillation column during the distillation process, the bottom liquid becomes high boiling point, the temperature of the bottom fraction rises and the residue Increased viscosity. As a result, industrial distillation is difficult. In contrast, trimellitic anhydride is distilled and separated with a K-cycle distillation column bottom liquid. The paper size is applicable to Chinese National Standards (CNS) Λ4 gauge (210 × 297 公 #) ^ 577874 Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Distillation Explanation (5 liquids, the heat generated by meta-anhydride alkanoic acid ο ❾ ❾ Benzene heat or long-term dianhydride of the acid derived from the two W Sanli plus its 90Mr partial calorimetric ratio of hair column acid treatment to obtain three, ¾ benzene From up to CX, from the pure four-distillation three-hot pure, phenylbenzene, M, the heat of the boron 5003 ί in the thermal weight of the low-distilled benzene plus low-fruit partial δ water plus liquefaction to 25h anhydride and 3¾ The lower part of the production takes ¾ to remove the substrate oxygen under W acid to prevent and cause. Base 1? After the addition of heat under π 3. The pressure of three, and the acid storage anhydride However, the column was mixed and mixed under W benzene to reduce benzene containing isocaproic triboronic acid trilipids. "From, distillate anhydride reduced IL partial MW partial acid bias, benzoated triphenyl 4 ~ (i meridian The steamed acid is more acidic than M or OR. The organic partial oxidation of benzene is 2,17 or combined, and the three times f is more stable than the acid benzoated anhydride. Medium benzene is seeded with 1¾ amount of tristable metastable acid and acid. Hit III ’s partial sizing or ii heavy phthalic anhydride is low. There are three small factors due to the nature of the oxygen. The phthalic anhydride ring and the acetic acid are reduced to benzene heat. Benzene is best supplied by partial acid and hot acid, or pirate. Three sulphur is because of partial supply, high demand for levy ^ Administering three grades plus three οο ί succinic acid is described as benzene, and the quality is also crude. Even the boron benzene is $ 2u, and the lower polarized distillate should be acidic and hot, and the amount of partial benzene is used to obtain a high oxygen vaporization, and then the reverse production of three or three M is added, so that or i may contain the boron. Production step. The amount of acid in the acid column under the raw phenylhydrazone was depressurized. The human acid was added to the physiological point to subtract the material, sugar and pressure three distillation. The Ming San U β column was added to the distillate after the Ming San filling. Among them, aldehyde reduction benzene steaming benzene 0 * 5 distillation in benzene benzene, but the original hot high-temperature steaming acidic acid expression, the French A in the partial progress and three partial efforts to steam the base, partial, the acid is more than three times after the replacement of benzene and boron. Lemma Yum enters the acid and then the water and the lower body are mixed with the benzene three. The degree of PP of the radical is at the time of desorption. M benzene ---- 2-^-i-:- ; (Please read the notes on the back before filling in this purchase) • 丨 Order- ----- 1 j-—I— HJ. This paper size applies to Chinese National Standard (CNS) Λ4 gauge (210X 297 public dream 577874 A7 B7 V. Description of the invention (6) In other words, the fourth invention provides a Method for producing trimellitic anhydride by oxidizing 1,2,4-aliphatic substituted benzene, dialkylbenzaldehyde and / or oxide intermediate thereof to produce trimellitic anhydride, the method comprising heat-treating trimellitic acid or trimellitic acid The mixture of acid and trimellitic anhydride obtained by dehydrating trimellitic acid by heating until the content of trimellitic acid based on the total amount of trimellitic acid and trimellitic acid is 3¾ weight ratio or M, and the heat-treated product is introduced into the distillation column. It is preferred that under heat treatment conditions, the pressure is reduced to 200 Torr or M, the temperature is at least 250 ° C, and the processing time is at least 30 minutes. Brief Description of the Drawings Figure 1 shows an example of a flowchart of a method for preparing trimellitic anhydride provided by the third invention. Detailed description of the invention The dialkyl aromatic aldehydes used in the oxidation raw materials of the first and second inventions include 2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde and 3,4-dimethyl Benzaldehyde. Its oxide derivatives include 2,4-dimethylbenzoic acid, 2,5-dimethylbenzoic acid, 3,4-dimethylbenzoic acid, formamylmethylbenzoic acid and methylphthalic acid. Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of Didi (Read the precautions before filling this page) The low-carbon aliphatic carboxylic acid used as a solvent in the aforementioned oxidation is an aliphatic one containing 1 to 5 carbon atoms. A carboxylic acid, which may be selected from formic acid, acetic acid, propionic acid, butyric acid, or a mixture thereof. M acetic acid and propionic acid are preferred, and M acetic acid is particularly preferred. The water content of the solvent is 5 to 70 ¾ by weight, preferably 10 to 60 ¾ by weight. When the water content is lower than the aforementioned lower limit, trimellitic acid and heavy gold sulfonium salts are easily formed, and thus the catalyst activity is reduced. When the water content is higher than the aforementioned upper limit, the reaction rate decreases, so the yield is low. The amount of solvent p-dialkyl aromatic aldehyde and its oxide derivatives is usually 1 This paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210X 297 public #) 9 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 577874 A7 B7 5. Description of the invention (7) to 20 times, preferably 3 to 10 times. The oxide of the first invention uses heavy metal rhenium as a catalyst, and manganese alone or manganese and cobalt as a catalyst. The oxidation of the second invention uses a bromine-manganese-based catalyst as a catalyst. These manganese, cobalt, and hafnium compounds include organic salts, halides and carbonates. In particular, it is preferably used in the form of an acetate or a bromide. The bromine compound used as the oxidation catalyst is not particularly limited as long as it does not dissolve the reaction system and generate bromine ions. Bromine compounds include inorganic bromine such as hydrogen bromide, sodium bromide and cobalt bromide, and organic bromine such as tetrabromoethane. In particular, hydrogen bromide, cobalt bromide and manganese bromide are preferred. According to the second invention, zirconium and hafnium are added to the manganese-bromine system catalyst. In this example, the catalyst activity is increased and the reaction rate is greatly improved. It is particularly preferred to add zirconium and 钸 0 heavy metals to the solvent at a concentration of 0.03 to 2¾ by weight, preferably from 0,05 to U by weight. When the catalyst concentration is lower than the lower limit of the former 逑, no reaction is performed. When the catalyst concentration exceeds the aforementioned upper limit, the catalyst adversely affects the reaction. Manganese is usually used as imitation heavy metal, while cobalt is used as part of heavy metal. When zirconium and hafnium are added to manganese, the composition of heavy metals is better as follows. Based on the total amount of heavy metals, the zirconium content is 1 to 10¾ by weight, the hafnium content is 1 to 20¾ by weight, and the manganese content is 70 to 98¾ by weight. 1 至 1¾ 重量 比。 The bromine concentration of the solvent is from 0.05 to 2¾ by weight, preferably from 0.1 to 1¾ by weight. When the bromine concentration is lower than the aforementioned lower limit, the reaction cannot proceed. When the bromine concentration is higher than the aforementioned upper limit, severe corrosion occurs. The atomic ratio of heavy metal catalyst to bromine anion is 0.5 to 10, preferably 0.8 to _____ This paper size is applicable to Chinese National Standard (CNS) Λ4% Taiwan (210X297々 $)-10-(Please read first (Notes on the back then fill out this page)
577874 A7 經滴部中央標率局貝工消費合作社印¾ B7五、發明説明（8 ) 氧化用之含氧氣體包括氧氣及氧氣與惰性氣體如氮或氬 之混合物。最常使用空氣。 氧化反應器係選自攪拌容器或發泡柱，但攪拌容器為較 佳可供充份於反應器内攪拌。反應程序較佳為半批次或連 攮方法。半批次方法中，較佳於原料進料中止後繼壤供給 含氧氣體5至60分鐘俾完成氧化◊連續方法中，較佳提供 複數串聯反應器供改良反應產率。 氧化溫度為180至240 1C，較佳190至230 t!。於前述範圍 K外之氧化溫度，副產物含量增高而偏苯三酸產率低。 氧化中，含氧氣體連缅供給反應器，反應後氣體連績撤 出故壓力為5至40kg/cm2，較佳10至30kg/crn2。來自反應 器之排放氣體之氧濃度為0.1至8¾容積比，較佳1至5¾容積 比〇 反應器設置回流冷凝器供冷凝排放氣體所含大量溶劑及 氧化產生之水。冷凝溶劑及水通常循環至反應器，而部份 由反應系統撤出供調整反應器之水濃度。 反應液體於反應器之停留時間通常為0.5至5小時。當複 數反應器於串聯設置時，前述停留時間為於複數反應器之 停留時間和。 得自氧化之反應混合物冷卻至約1 0 °C至1 2 0 °C之溫度， 較佳約20 °C至40 °C之溫度，所得晶體藉過濾或離心分離於 反應混合物分開。分離之偏苯三酸粗晶再調成漿液清洗或 Μ水清洗或含水乙酸清洗而去除晶體所含有機雜質、金靨 等0 本紙張尺度適用中國國家標準（CNS ) Λ4規枱（210Χ 297公铃） ——^-裝——— · (請先閱讀背面之注意事項再填寫本頁)577874 A7 Printed by Shelley Consumer Cooperatives, Central Standards Bureau of Drip Department ¾ B7 V. Description of the invention (8) Oxygen-containing gas used for oxidation includes oxygen and a mixture of oxygen and an inert gas such as nitrogen or argon. Air is most often used. The oxidation reactor is selected from a stirred vessel or a foamed column, but a stirred vessel is preferred to be fully stirred in the reactor. The reaction procedure is preferably a semi-batch or continuous method. In the semi-batch process, it is preferable to supply the oxygen-containing gas for 5 to 60 minutes after the feedstock is stopped, and to complete the continuous process of dysprosium oxide, it is preferable to provide a plurality of reactors in series for improving the reaction yield. The oxidation temperature is 180 to 240 1C, preferably 190 to 230 t! At oxidation temperatures outside the aforementioned range K, the content of by-products increases and the yield of trimellitic acid is low. During the oxidation, oxygen-containing gas is continuously supplied to the reactor, and the gas is continuously withdrawn after the reaction, so the pressure is 5 to 40 kg / cm2, preferably 10 to 30 kg / crn2. The oxygen concentration of the exhaust gas from the reactor is 0.1 to 8¾ volume ratio, preferably 1 to 5¾ volume ratio. The reactor is provided with a reflux condenser for condensing a large amount of solvent contained in the exhaust gas and water generated by oxidation. The condensed solvent and water are usually circulated to the reactor, and part of it is withdrawn from the reaction system for adjusting the water concentration of the reactor. The residence time of the reaction liquid in the reactor is usually 0.5 to 5 hours. When a plurality of reactors are arranged in series, the aforementioned residence time is the sum of the residence times of the plurality of reactors. The reaction mixture obtained from the oxidation is cooled to a temperature of about 10 ° C to 120 ° C, preferably about 20 ° C to 40 ° C. The obtained crystals are separated by filtration or centrifugation in the reaction mixture. The separated trimellitic acid coarse crystals are then adjusted to slurry cleaning or M water cleaning or aqueous acetic acid cleaning to remove organic impurities, gold tints, etc. contained in the crystals. This paper size is applicable to the Chinese National Standard (CNS) Λ4 gauge (210 × 297 mm) Bell) —— ^-装 ——— · (Please read the notes on the back before filling in this page)
、1T έ I i· - j --- 經滴部中央標準局負工消費合作社印製 577874 A7 B7 五、發明説明（9 ) 氧化較佳連壤進行，連續方法中，由反應混合物分離偏 苯三酸晶體後，大半反應母液循環至氧化系統。部份反應 母液被蒸餾供去除生成之水而其餘用做溶劑。 根據第一發明之偏苯三酸晶體含極小量重金屬及具有極 高純度，故偏苯三酸酐可藉加熱直接脫水獲得而無需任何 純化步驟。 換言之，當二烷基芳族醛及/或其氧化物衍生物於根據 第一發明之含規定量水之低碳脂族羧酸溶劑氧化時，可K 高產率獲得偏苯三酸晶體，其中重金鼷濃度極低。故晶體 回收後，大部份含重金屬及溴之催化劑成份含有母液，前 述母液循環至氧化反應器因而循環催化劑。 因此，於本發明方法可降低生產偏苯三酸之催化劑成本 ，容易純化偏苯三酸。結果，也可降低回收催化劑成本做 為防止環境污染之成本。 根據第一發明之方法，可降低溴於催化劑成份之濃度因 而反應器無需使用特用材料。 第二發明中，含鍩及鈽之一或之二之錳-溴系統催化劑 具有比習知鈷-錳-溴系統催化劑更高的催化劑活性；當二 烷基芳族醛及/或其氧化物衍生物於前述催化劑存在下於 規定範圍之含水低碳脂族狻酸溶劑氧化時，可Μ高產率連 續生產偏苯三酸。 習知難Μ達成之連續生產偏苯三酸可根據本發明進行， 可Μ高產率獲得偏苯三酸及生成之中間物量小。因此偏苯 三酸可顯著優異地於業界生產，故本發明於業界具有重大 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X2^7公蝥） (請先閱讀背面之注意事項再填寫本頁 一裝·、 1T I I ·-j --- Printed by the Ministry of Standards, Central Standards Bureau, Consumer Cooperatives 577874 A7 B7 V. Description of the invention (9) Oxidation is preferably carried out on the contiguous side. In a continuous method, the partial benzene is separated from the reaction mixture. After the three acid crystals, most of the reaction mother liquor is circulated to the oxidation system. Part of the reaction mother liquor is distilled to remove the generated water and the rest is used as a solvent. The trimellitic acid crystal according to the first invention contains a very small amount of heavy metals and has extremely high purity, so trimellitic anhydride can be directly dehydrated by heating without any purification step. In other words, when the dialkyl aromatic aldehyde and / or its oxide derivative is oxidized in a low-carbon aliphatic carboxylic acid solvent containing a prescribed amount of water according to the first invention, trimellitic acid crystals can be obtained in high yield, where The concentration of heavy gold tincture is extremely low. Therefore, after the crystals are recovered, most of the catalyst components containing heavy metals and bromine contain mother liquor, and the mother liquor is circulated to the oxidation reactor to circulate the catalyst. Therefore, in the method of the present invention, the cost of a catalyst for producing trimellitic acid can be reduced, and trimellitic acid can be easily purified. As a result, the cost of recovering the catalyst can be reduced as a cost for preventing environmental pollution. According to the method of the first invention, the concentration of bromine in the catalyst component can be reduced so that the reactor does not need to use special materials. In the second invention, the manganese-bromine system catalyst containing one or both of thorium and thorium has higher catalyst activity than the conventional cobalt-manganese-bromine system catalyst; when the dialkyl aromatic aldehyde and / or its oxide When the derivative is oxidized in the presence of the aforementioned catalyst in an aqueous low-carbon aliphatic phosphonic acid solvent, trimellitic acid can be continuously produced in high yield. The continuous production of trimellitic acid, which is difficult to achieve, can be performed according to the present invention, and trimellitic acid can be obtained in high yield and the amount of intermediates produced is small. Therefore trimellitic acid can be produced significantly in the industry. Therefore, the invention has a significant paper size in the industry. Applicable to China National Standard (CNS) Λ4 specification (210X2 ^ 7mm). (Please read the precautions on the back before filling in this. One page installed ·
J~~ m Ί - Μ II Ί I !τ -I I 一 12 - 577874 A7 B7 五、發明説明（10 ) 意義。 (請先閱讀背面之注意事項再填寫本頁) 於第三及第四發明用於純化之偏苯三酸係藉氧化1 , 2 , 4-脂族基取代苯，二烷基苯甲醛及其氧化中間物生產。氧化 原料之特例包括1,2 ,4-三甲基苯，2,4-二烷基苯甲醛，2, 5-二烷基苯甲醛，3, 4-二烷基苯甲醛及其氧化中間物如2, 4-二烷基苯羧酸，2,5-二烷基苯羧酸，3,4-二烷基苯狻酸 用含5¾或Μ下雜質其 劑如錳於脂族基取代 態氧氧化前逑氧化原 甲基苯或2,4-二甲基 存在之催化劑存在下 水或含水乙酸溶劑氧 續法之任一種進行* 而第三及第四發明較 行，故偏苯三酸於偏 為3¾:重量比或Μ下， 一個容器内進行時， 苯三酸脫水比。因此 階段及逐步提高脫水 水係於2 0 0至3 0 0 °C之 等。氧化原料無須具1 0 0 純度，可使 不會藉氧化形成偏苯三酸之原料。 偏苯三酸可經由於重金屬氧化催化 苯之液相氧化存在下使用分子氧或氣 料獲得。特別，前述原料如1,2, 4-三 苯甲醛於催化劑其中重金屬及溴共同 於200 °C至2801C之溫度使用分子氧於 化。氧化可藉批次法、半連續法及連 但業界最佳使用連續氧化法。 經滴部中央標率局貝工消費合作社印製 偏苯三酸係藉前述液相氧化獲得， 佳於蒸餾前藉加熱脫水粗偏苯三酸進 苯三酸與偏苯三酸酐之混合物之含量 較佳0至1 ϋί重量比。 當脫水係於減壓下或於大氣壓下於 極難Κ如前逑蒸發由粗偏苯三酸之偏 ，較佳將脫水反應器劃分成至少二個 比。 例如，第一脫水反應器中，加熱脫 本紙張尺度適用中國國家標準（CNS)Λ4規枱（ 210x 297公f) -13 — 577874 經滴部中央標準局貝工消費合作社印製 A7 B7五、發明説明（11 ) 溫度於大氣壓下或減壓下進行而未對操作產生任何影響； 第二脫水反應器中，脫水係於200托耳或以下，較佳100托 耳或K下之減壓下進行，而未脫水之偏苯三酸含量調整至 3¾或Μ下。 第二脫水反應器（加熱處理容器）中，加熱處理易於同溫 進行，因此有色成份被轉成具有高沸點之成份。至於將有 色成份轉成具有高沸點成份之條件需要於250 10或以上進 行加熱處理至少5分鐘。較佳溫度為250 °C至300 °C之範圍 ，溫度越高，加熱處理所需時間越短。但，當溫度高於300 °C時，偏苯三酸酐之分解反應無法忽略。當前述加熱處理 係於減壓下進行時，有色成份轉成具高沸點成份而可藉蒸 餾去除。 第三發明中，為了縮短加熱處理停留時間，硼之氧化物 典型例為正硼酸，偏硼酸，四硼酸及氧化硼添加至脫水反 應器。至於添加方法可呈固體形式引進，或可圼水溶液形 式添加。 硼氧化物於蒸餾柱之柱底液體於加熱處理步驟後之蒸餾 步驟濃縮時，將柱底液體轉成具有高沸點液體。因此硼氧 化物係添加改良品質所需之最小量。 換言之，硼氧化物新進添加之重量比基於偏苯三酸經常 為 50 至 900ppib，較佳 50 至 300ρριπ° 底液所含硼氧化物被失活化而對加熱處理影響極小。前 述硼氧化物之重量比為於循環之蒸餾柱底液中未含硼氧化 物之值。 本紙張尺度適用中國國家標準（CNS ) Λ4規掊（210Χ29?公筇） -14 一 (請先閲讀背面之注意事項再填寫本頁) 一裝_ 、1Τ Φ 577874 kl B7 五、發明説明（l2 ) 於加熱處理容器內足夠將有色成份轉成高沸點成份之停 留時間於連績法至少5分鐘，可依據加熱處理溫度選擇。 如前逑，加熱處理進行至將有色成份全然轉成高沸成份 ，然後進行蒸餾獲得偏苯三酸酐。蒸餾係於50托耳或以下 之減壓下進行。蒸餾時，具高沸點物質藉單純蒸餾分離， 而可進行精餾俾獲得較高效率。 第三發明中，當蒸餾期間部份蒸餾柱之柱底液循環至加 熱處理容器及進行循環操作時，加熱處理後蒸餾步驟之蒸 餾柱柱底液濃縮程度下降，因此可避免因硼氧化物造成柱 底液轉成高沸液體。當柱底液循環至加熱處理容器時，出 乎意外地柱底液所含硼氧化物被失活化，因此可抑制柱底 液轉成高沸液體，可進行蒸餾而毫無殘餘問題。為了防止 轉成具高沸點液體，基於粗偏苯三酸，待循環至加熱處理 容器之柱底液量至少為10¾重量比，較佳至少20¾重量比。 經滴部中央標率局員工消費合作社印裂 (請先閲讀背面之注意事項再填寫本頁) 將參照附圖說明第三發明。附圖顯示根據第三發明生產 偏苯三酸酐之方法之流程圖。經由氧化1，2，4-脂族基取代 苯，二烷基苯甲醛及其氧化物中間物所得偏苯三酸係經由 管線1引進脫水反應器2。脫水反應器中，加熱脫水係於大 氣壓下進行而脫水偏苯三酸。偏苯三酸與偏苯三酸酐之混 合物經管線3引進加熱處理4。又，硼氧化物經由管線5引 進加熱處理容器，又，不僅脫水，同時加熱處理係於減壓 下進行而將有色成份轉成高沸點成份。 得自加熱處理容器之偏苯三酸及偏苯三酸酐混合物經管 線6引進蒸餾柱7，高品質偏苯三酸酐被蒸餾出並經管線撤 本紙張尺度適用中國國家標準（CNS ) Λ4規枱（210X 297公焓） 一 15 — 經滴部中央標準局員工消費合作社印製 577874 A7 B7 五、發明説明（13 ) 出由蒸餾柱頂部份分離。脫水形成之水藉氣體經管線9攜 帶至真空泵。高沸點物質經管線1 0由蒸餾柱底撤出。部份 蒸餾柱底液經管線11循環至加熱處理容器4，其用來防止 因底液濃縮時底液轉成高沸液體引發之問題，可穩定地獲 得具高品質之偏苯三酸酐。 根據第三發明，於粗偏苯三酸脫水接近完成後，於所需 最小量之硼氧化物存在下於減壓下進行加熱處理，因而將 有色成份轉成高沸點成份。藉蒸餾純化可降低偏苯三酸酐 色度，同時偏苯三酸酐純度增高。又，經由循環蒸餾柱底 液至加熱處理容器，可防止底液轉成高沸點液體至較大程 度，可毫無殘餘問題進行蒸餾。 第四發明中，於液相藉氧化所得偏苯三酸經加熱脫水故 偏苯三酸於偏苯三酸與偏苯三酸酐混合物之含量為3¾或以 下，較佳0至1 %。 但，如前述，當脫水係於為減壓或大氣壓下於單一容器 内進行時極難Μ提高得自粗偏苯三酸之偏苯三酸脫水比。 因此較佳將脫水反應器劃分成至少二階段俾逐步增高脫水 比〇 例如，於第一脫水反應器中，加熱脫水係於大氣壓或減 壓下於200至300 °C溫度進行而對操作無影響；第二脫水反 應器中，脫水係於200托耳或以下，較佳100托耳或以下之 減壓下進行因而未脫水之偏苯三酸含量調整至3¾或以下。 第二脫水反應器（加熱處理容器）中，也同時進行加熱處 理，因此有色成份轉成高沸成份。至於有色成份轉成高沸 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210Χ297ϋ ) ^ -16 - I 裝--.-- (請先閱讀背面之注意事項再填寫本頁) - -- - - - - f 、v5 έ 經漓部中央標準局員工消費合作社印製 577874 A7 B7 五、發明説明（I4 ) 成份之條件，需於2 5 0 °C或以上進行加熱處理。加熱處理 較佳於250 °C至300 °C之範圍進行，溫度越高則加熱處理所 需時間越短。但，當溫度高於300 °C時，偏苯三酸酐之分 解無法忽略。當前述加熱處理係於減壓下進行時，有色成 份轉成高沸成份而可藉蒸餾去除。 第四發明之特徼為加熱處理係於減壓下長時間進行而未 添加硼氧化物至加熱處理容器。連纊方法中，加熱處理停 留時間要求至少30分鐘，可依據加熱處理溫度選擇。 加熱處理至有色成份完全轉成高沸成份，進行蒸餾獲得 偏苯三酸酐。至於蒸餾絛件，蒸餾係於50托耳或Μ下及減 壓下進行。蒸餾時，高沸物質藉單純蒸餾分雛，而精餾可 Κ較高效率進行。 根據第四發明，於粗偏苯三酸脫水接近完成後，長時間 進行加熱處理將有色成份轉成高沸成份，及藉蒸餾純化因 而降低偏苯三酸酐色度，提高偏苯三酸酐純度及毫無殘餘 問題進行蒸餾。 前述第三及第四發明中，脫水，加熱處理及蒸餾可藉批 次法、半批次法及練續法之任一者進行，以連續法為佳。 根據本發明方法，即使具低純度原料生產之偏苯三酸品 質改良，仍可穩定獲得高品質偏苯三酸酐。 較佳具體例之說明 將參照後文實例特別說明本發明。本發明絕非限於此等 實例。 表2中，ΤΜΑ表示偏苯三酸。產率表示基於芳族醛做原料 本紙張尺度適用中國國家標準（CNS ) Λ4規格（21〇X297々>¥ ) —^ϋ tut im— Βι^ϋ ^ϋ·_ϋ ·>111_1 1^11 \ / m^i ^ϋϋ tl·—^ ϋι.^1 1—BLri ih tammMl ea^Kiw ϋ·ι_^— —^ϋ i^ni >1_1 ·ϋϋ« ϋϋ ϋ^— ^ϋϋ —ν^ϋ (請先閱讀背面之注意事項再填寫本頁) -17 — 577874 A7 B7 五、發明説明（l5 ) 之偏苯三酸或氧化物中間物（一羧酸，二羧酸）之產物量（ 莫耳比）。 (請先閱讀背面之注意事項再填寫本頁) 實例1至3及比較例1 (第一發明） 鈦製成之高壓蒸氣鍋配備有具回流冷凝器之排氣管，進 氣管，原料連續進料流及攪拌器餵進1,01 Og催化劑溶液， 其係經由混合乙酸鈷四水合物，乙酸錳四水合物，47wti： 溴化氫水溶液，冰醋酸及水製備，其含鈷含量0. 11 6¾重量 比，錳含量0 . 11 7 %重量比及溴含量0 . 5 重量比，其水含量 改變接著進料1348/^之2,4-二甲基苯甲醛及8088/}1之具前 述濃度之催化劑溶液。反應係於3 2 k g / c in2 G壓力於2 3 0 °C溫 度進行，廢氣氧化量為2¾容積比。反應產物被連績撤出而 維持液面於恆定高度。所得反應產物冷卻至30TC及過濾分 離晶體。晶體於50它使用具有晶體重量之乙酸清洗。所得 晶體經乾燥，濾液及洗液分析獲得產率及晶體含所含金靥 ϋ表1顯τρ：结果。 表1 經满部中央標準局貝工消費合作社印製J ~~ m Ί-Μ II Ί I! Τ -I I-12-577874 A7 B7 V. Explanation of the invention (10) Significance. (Please read the precautions on the back before filling this page) The trimellitic acid used for purification in the third and fourth inventions is based on oxidation of 1, 2, 4-aliphatic substituted benzene, dialkylbenzaldehyde and its Oxidative intermediate production. Specific examples of raw materials for oxidation include 1,2,4-trimethylbenzyl, 2,4-dialkylbenzaldehyde, 2,5-dialkylbenzaldehyde, 3,4-dialkylbenzaldehyde and their oxidation intermediates Such as 2,4-dialkylbenzenecarboxylic acid, 2,5-dialkylbenzenecarboxylic acid, 3,4-dialkylphenylcarboxylic acid with 5¾ or M impurities, such as manganese in aliphatic substituted state Before the oxygen oxidation, either oxidize orthomethylbenzene or 2,4-dimethyl in the presence of a catalyst in the presence of water or an aqueous acetic acid solvent. Oxygen continuation method is carried out. * The third and fourth inventions are better, so trimellitic acid is Partially 3¾: weight ratio or M, when carried out in a container, the trimellitic acid dehydration ratio. Therefore, the dehydration system is gradually increased at a temperature between 2000 and 300 ° C. The oxidation raw material does not need to have a purity of 100, so that the raw material which does not form trimellitic acid by oxidation can be used. Trimellitic acid can be obtained using molecular oxygen or gas in the presence of heavy metal oxidation catalyzed liquid phase oxidation of benzene. In particular, the aforementioned raw materials such as 1,2,4-tribenzaldehyde are used in the catalyst in which heavy metals and bromine are co-oxidized at a temperature of 200 ° C to 2801C using molecular oxygen. Oxidation can be performed by batch, semi-continuous, and continuous methods, but continuous oxidation is the best method in the industry. The trimellitic acid is printed by the above-mentioned liquid-phase oxidation, printed by Shelley Consumer Cooperative of Dibei Central Standard Bureau, and it is better than heating and dehydrating crude trimellitic acid into the mixture of trimellitic acid and trimellitic anhydride before distillation. To 1 ϋί weight ratio. When the dehydration system is under reduced pressure or at atmospheric pressure, it is extremely difficult to evaporate from the crude trimellitic acid, as described above, it is preferable to divide the dehydration reactor into at least two ratios. For example, in the first dehydration reactor, the size of the paper used for heating is applicable to the Chinese National Standard (CNS) Λ4 gauge (210x 297 gf) -13 — 577874. Printed by the Shell Standard Consumer Cooperative, A7, B7. Description of the invention (11) The temperature is carried out at atmospheric pressure or reduced pressure without any impact on the operation; in the second dehydration reactor, the dehydration is at 200 Torr or lower, preferably at 100 Torr or K at a reduced pressure Proceed without trimming the trimellitic acid content to 3¾ or M. In the second dehydration reactor (heat treatment container), the heat treatment is easily performed at the same temperature, so the colored components are converted into components having a high boiling point. As for the condition for converting the colored component to a component having a high boiling point, it is necessary to perform a heat treatment at 250 to 10 or more for at least 5 minutes. The preferred temperature is in the range of 250 ° C to 300 ° C. The higher the temperature, the shorter the time required for heat treatment. However, when the temperature is higher than 300 ° C, the decomposition reaction of trimellitic anhydride cannot be ignored. When the aforementioned heat treatment is performed under reduced pressure, the colored components are converted into components with high boiling points and can be removed by distillation. In the third invention, in order to shorten the heat treatment residence time, typical examples of boron oxides are orthoboric acid, metaboric acid, tetraboric acid, and boron oxide, which are added to the dehydration reactor. As for the addition method, it can be introduced as a solid form, or it can be added as an aqueous solution. The liquid at the bottom of the boron oxide in the distillation column is concentrated in the distillation step after the heat treatment step, and the liquid at the bottom of the column is converted into a liquid having a high boiling point. Therefore, the minimum amount of boron oxide required to improve quality is added. In other words, the weight ratio of newly added boron oxide based on trimellitic acid is often 50 to 900ppib, preferably 50 to 300ρριπ °. The boron oxide contained in the bottom liquid is deactivated and has little effect on the heat treatment. The aforementioned weight ratio of boron oxide is a value that does not contain boron oxide in the circulating bottom liquid of the distillation column. This paper size applies Chinese National Standards (CNS) Λ4 Regulations (210 × 29?) -14 I (Please read the precautions on the back before filling this page) One Pack _, 1T Φ 577874 kl B7 V. Description of the Invention (l2 ) The residence time in the heat treatment container sufficient to convert the colored components to high boiling point components is at least 5 minutes in the continuous method, which can be selected according to the heat treatment temperature. As before, the heat treatment is performed until the colored components are completely converted into high boiling components, and then the trimellitic anhydride is obtained by distillation. Distillation is performed at a reduced pressure of 50 Torr or less. During distillation, substances with high boiling points can be separated by simple distillation, and rectification can be performed to obtain higher efficiency. In the third invention, when part of the column bottom liquid of the distillation column is circulated to the heat treatment container and the circulation operation is performed during the distillation, the degree of concentration of the bottom liquid of the distillation column in the distillation step after the heat treatment is reduced, so it can be avoided due to boron oxide The bottom of the column turned into a high boiling liquid. When the column bottom liquid is circulated to the heat treatment vessel, the boron oxide contained in the column bottom liquid is unexpectedly deactivated, so the column bottom liquid can be inhibited from turning into a high boiling liquid, and distillation can be performed without residual problems. In order to prevent conversion to a liquid with a high boiling point, based on the crude trimellitic acid, the amount of liquid at the bottom of the column to be recycled to the heat treatment vessel is at least 10¾ by weight, preferably at least 20¾ by weight. Printed by the Consumers Cooperative of the Central Standards Bureau of Dibei (please read the precautions on the back before filling this page) The third invention will be explained with reference to the drawings. The drawing shows a flowchart of a method for producing trimellitic anhydride according to the third invention. Trimellitic acid, which is obtained by oxidizing 1,2,4-aliphatic substituted benzene, dialkylbenzaldehyde and its oxide intermediate, is introduced into dehydration reactor 2 through line 1. In the dehydration reactor, heating dehydration is performed under atmospheric pressure to dehydrate trimellitic acid. The mixture of trimellitic acid and trimellitic anhydride is introduced into the heat treatment 4 through the pipeline 3. In addition, boron oxide is introduced into the heat treatment container through line 5, and not only dehydration, but also heat treatment is performed under reduced pressure to convert colored components into high boiling point components. The trimellitic acid and trimellitic anhydride mixture obtained from the heat-treated container is introduced into the distillation column 7 through the pipeline 6. The high-quality trimellitic anhydride is distilled off and removed through the pipeline. This paper applies the Chinese National Standard (CNS) Λ4 gauge (210X 297 enthalpy) I 15 — Printed by the Consumers Cooperative of the Central Standards Bureau of Didi Ministry 577874 A7 B7 5. Description of the invention (13) The product is separated by the top part of the distillation column. The water formed by the dehydration is carried by the gas to the vacuum pump through the line 9. High-boiling substances are withdrawn from the bottom of the distillation column through line 10. Part of the bottom liquid of the distillation column is circulated to the heat treatment container 4 through the line 11 to prevent the problem caused by the bottom liquid being converted to a high boiling liquid when the bottom liquid is concentrated, and high-quality trimellitic anhydride can be obtained stably. According to the third invention, after the dehydration of the crude trimellitic acid is almost completed, the heat treatment is performed under reduced pressure in the presence of the required minimum amount of boron oxide, thereby converting the colored components into high-boiling components. Purification by distillation can reduce the color of trimellitic anhydride and increase the purity of trimellitic anhydride. In addition, by circulating the bottom liquid of the distillation column to the heat treatment vessel, the bottom liquid can be prevented from being converted to a high boiling point liquid to a large extent, and distillation can be performed without residual problems. In the fourth invention, the trimellitic acid obtained by oxidation in the liquid phase is dehydrated by heating so that the content of trimellitic acid in the mixture of trimellitic acid and trimellitic anhydride is 3¾ or less, preferably 0 to 1%. However, as described above, it is extremely difficult to increase the trimellitic acid dehydration ratio derived from crude trimellitic acid when the dehydration is performed in a single container under reduced pressure or atmospheric pressure. Therefore, it is better to divide the dehydration reactor into at least two stages and gradually increase the dehydration ratio. For example, in the first dehydration reactor, the heating dehydration is performed at atmospheric pressure or reduced pressure at 200 to 300 ° C without affecting the operation. In the second dehydration reactor, the dehydration is performed at a reduced pressure of 200 Torr or less, preferably 100 Torr or less, so that the trimellitic acid content that is not dehydrated is adjusted to 3¾ or less. In the second dehydration reactor (heat treatment container), heat treatment is also performed at the same time, so the colored components are converted into high boiling components. As for the conversion of colored components into high boiling paper, the Chinese National Standard (CNS) Λ4 specification (210 × 297ϋ) ^ -16-I Pack --.-- (Please read the precautions on the back before filling this page)--- ---f, v5 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Lithuania 577874 A7 B7 V. Description of the Invention (I4) The conditions of the ingredients need to be heated at 250 ° C or above. The heat treatment is preferably performed at a temperature of 250 ° C to 300 ° C. The higher the temperature, the shorter the time required for the heat treatment. However, at temperatures above 300 ° C, the decomposition of trimellitic anhydride cannot be ignored. When the aforementioned heat treatment is performed under reduced pressure, the colored components are converted into high boiling components and can be removed by distillation. A feature of the fourth invention is that the heat treatment is performed under reduced pressure for a long time without adding boron oxide to the heat treatment container. In the flail method, the heat treatment residence time is required to be at least 30 minutes, which can be selected according to the heat treatment temperature. Heat treatment until the colored components are completely converted to high boiling components, and distillation is performed to obtain trimellitic anhydride. As for the distillation unit, the distillation was performed at 50 Torr or M under reduced pressure. During distillation, high-boiling substances are separated by simple distillation, and rectification can be performed with higher efficiency. According to the fourth invention, after the dehydration of the crude trimellitic acid is nearly completed, the long-term heat treatment is used to convert the colored components into high-boiling components, and the distillation is purified to reduce the color of trimellitic anhydride, improve the purity of trimellitic anhydride and perform distillation without residual problems . In the aforementioned third and fourth inventions, the dehydration, heat treatment, and distillation may be performed by any of a batch method, a semi-batch method, and a continuous method, and a continuous method is preferred. According to the method of the present invention, even if the quality of trimellitic acid produced with low-purity raw materials is improved, high-quality trimellitic anhydride can be obtained stably. DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described with reference to the following examples. The invention is by no means limited to these examples. In Table 2, TMA represents trimellitic acid. Yield is based on aromatic aldehydes as raw materials. The paper size applies Chinese National Standard (CNS) Λ4 specifications (21〇X297々 > ¥) — ^ ϋ tut im— Βι ^ ϋ ^ ϋ · _ϋ · > 111_1 1 ^ 11 \ / m ^ i ^ ϋϋ tl · — ^ ϋι. ^ 1 1—BLri ih tammMl ea ^ Kiw ϋ · ι _ ^ — — ^ ϋ i ^ ni > 1_1 · ϋϋ «ϋϋ ϋ ^ — ^ ϋϋ —ν ^ ϋ (Please read the precautions on the back before filling this page) -17 — 577874 A7 B7 V. Amount of product of trimellitic acid or oxide intermediate (monocarboxylic acid, dicarboxylic acid) in the description of the invention (l5) (Mo Ear ratio). (Please read the precautions on the back before filling this page) Examples 1 to 3 and Comparative Example 1 (First invention) The high-pressure steam cooker made of titanium is equipped with an exhaust pipe with a reflux condenser, an intake pipe, and continuous raw materials The feed stream and the stirrer were fed with 1,01 Og of a catalyst solution, which was prepared by mixing cobalt acetate tetrahydrate, manganese acetate tetrahydrate, 47wti: an aqueous solution of hydrogen bromide, glacial acetic acid and water, containing a cobalt content of 0. 11 6¾ weight ratio, manganese content 0.111% weight ratio and bromine content 0.5 weight ratio, the water content of which is changed, and then fed with 1,348 / ^ of 2,4-dimethylbenzaldehyde and 8088 /} 1 Catalyst solution of the aforementioned concentration. The reaction was performed at a pressure of 32 k g / c in2 G at a temperature of 230 ° C, and the amount of exhaust gas oxidation was 2¾ volume ratio. The reaction products were continuously withdrawn while maintaining the liquid level at a constant height. The resulting reaction product was cooled to 30TC and the crystals were separated by filtration. The crystals were washed at 50 with acetic acid with the weight of the crystals. The obtained crystals were dried, and the filtrate and washings were analyzed to obtain the yield and gold content contained in the crystals. Table 1 shows τρ: results. Table 1 Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards
Ex . 1 E x . 2 E x . 3 CEx . 1 溶劑之水含量 w t % 19 30 41 4 產率 m ο 1 % 90.6 91.1 90,6 76 . 9 晶體之鈷 ppm 470 140 15 5 , 290 晶體之錳 ppm 580 160 14 6 , 030 Εχ.=實例 CEx.=比較例 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X2W公费） 一 18- 577874 A7 B7 實例 五、發明説明（18Ex. 1 E x. 2 E x. 3 CEx. 1 Water content of solvent wt% 19 30 41 4 Yield m ο 1% 90.6 91.1 90,6 76. 9 Cobalt in crystal 470 140 15 5, 290 Manganese ppm 580 160 14 6, 030 Εχ. = Example CEx. = Comparative example This paper size applies Chinese National Standard (CNS) Λ4 specification (210X2W public expense) 18- 577874 A7 B7 Example V. Description of the invention (18
Zr (KOI 0 0 . 005 0 . 03 0 0 Ce 0 (KOI 0.005 0 . 03 0 0 Co 0 0 0 0 0 0.01 Μη 0*37 0.37 0 . 37 0 . 32 0.38 0 . 37 產率（Η! 0 m ΤΜΑ 89 . 1 87 . 1 89 . 8 91.0 80.0 83 . 8 中間物 3*5 7 + 9 4.0 3*5 10.4 6*7 C E X ,=比較例 實例1 1 重覆實例7，但2, 4-二甲基苯甲醛以2, 4-二甲基苯甲酸 替代及M 203g/h速率供給。所得偏苯三酸產率為92.0rooU ，及中間物產率為2 , 9 m ο 1 %。 實例12 重覆實例7，但2 , 4-二甲基苯甲醛以3 , 4-二甲基苯甲醛 替代及以1 8 2 g / h速率供給。所得偏苯三酸產率為8 8 . 1 hi ο 1 % ，及中間物產率為2 . 9 m ο 1 Si；。 比較例5 (第三發明） 根據JP-B-58 -22 22所述方法經由氧化2, 4-二甲基苯甲醛 所得粗偏苯三酸（偏苯三酸含量97, 5¾)以每小時1.5份之速 率連績供給脫水反應器，及於230 °C Μ停留時間3小時加熱 脫水。得自脫水反應器之偏苯三酸脫水比為90¾。然後， 得自脫水反應器之偏苯三酸與偏苯三酸酐之混合物於1 5托 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X 297公# ) I ~裝 „ ^ 訂 I (請先閱讀背面之注意事項再填寫本頁) 經满部中央標隼局員工消費合作社印製 -21 - 577874 A7 ΒΊ 五.、發明説明（19 ) 耳減壓下連續供給理論上具二階段之蒸餾柱，柱底液以每 小時3份速率連續測出。蒸餾柱係於15托耳減壓下於柱頂 溫250 °C及柱底溫250至260 °C操作，於穩態時柱頂及柱底 之溫差為1 0 t或以下。經蒸餾之偏苯三酸酐之純度為9 8 . 7 %，熔點為167 + 3°C及熔體色彩為APHA120。 偏苯三酸酐之熔體色彩係經由於大氣壓下於1 90 °C熔化 及比較熔化之偏苯三酸酐與JIS K1557-6.2所示APHA標準 液測定。 簧例1 3 經漓部中央標準局員工消費合作社印製 (讀先閱讀背面之注意事項再填寫本頁) 加熱處理容器置於比較例5使用之脫水反應器與蒸餾柱 間。於脫水反應器進行如同比較例5之程序。然後，10¾硼 酸水溶液Μ每小時0 . 1份速率供給加熱處理容器，加熱處 理容器之硼酸濃度達6 Op pm。然後，於50托耳減壓，260 °C 及1 0分鐘停留時間條件下進行脫水及加熱處理。得自加熱 處理容器之偏苯三酸脫水比為99 , 4¾。然後，得自加熱處 理容器之偏苯三酸與偏苯三酸酐之混合物連續供給理論具 二階段之蒸餾柱，柱底液Μ每小時3份速率連續撤出。20 份循環至加熱處理容器。蒸餾柱於1 5托耳減壓下，於柱頂 溫250 °C及柱底溫250至260 °C操作，穩態時，柱頂與柱底 間之溫差為101C或K下。由蒸餾柱蒸餾之偏苯三酸酐之純 度為99.2%，熔點167.4°〇及熔體色彩^1^80。加熱處理可 改良產物之偏苯三酸酐品質。 比較例6 經由氧化含94¾ 2, 4-二甲基苯甲醛，U甲基酞酸，U甲 本紙張尺度適用中國國家標準（CNS ) Λ4規枱（210X29D>i ) 577874 A7 五、發明説明（2〇 ) 基酞及U其它雜質之混合物所得粗偏苯三酸（偏苯三酸含 量96, U) Μ每小時150份之速率連續供給脫水反應器，及 於5 0 0托耳，2 3 5 °C及3 + 5小時停留時間之條件下加熱脫水 。得自脫水反應器之偏苯三酸脫水比為92¾。然後，得自 脫水反應器之含偏苯三酸及偏苯三酸酐之混合物連續供給 於1 5托耳減壓下理論上具四階段之蒸餾柱，柱底液係以每 小時3份速率連續撤出。於穩態下，柱頂與柱底溫差為1 0 °C或以下。蒸餾妥之偏苯三酸酐純度為98,6¾，熔點為167.3 °C及熔體色彩為APHA170。 比較例7 經漪部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 加熱處理容器置於比較例6使用之脫水反應器與蒸餾柱 間。於脫水反應器進行比較例6之相同程序。然後，10¾硼 酸水溶液K每小時0 . 4份速率供給加熱處理容器，加熱處 理容器之硼酸濃度達267ΡΡΙΠ，脫水及加熱處理係於50托耳 減壓，2 6 5 °C及停留時間5 0分鐘之條件下進行。由加熱處 理所得偏苯三酸脫水比為99 . 7¾。然後，得自加熱處理容 器之偏苯三酸與偏苯三酸酐之混合物供給理論具四階段之 蒸餾柱，柱底液Μ每小時3份速率連鑛撤出。蒸餾柱係於 1 5托耳減壓及柱頂溫2 5 0 °C操作。柱底液經濃縮，柱底溫 超過280 °C，柱頂與柱底間之溫差變30 °C或Μ上。因此難 以操作蒸餾柱。蒸餾妥之偏苯三酸酐具有純度99.2¾，熔 點1 6 7 . 5 °C及熔體色彩A P H A 1 0 0。加熱處理可改良產物之偏 苯三酸酐品質。 實例1 4 本紙張尺度適用中國國家標準（CNS ) Λ4規格（21〇X 297公發） -2 3 一 577874 Α7 Β7 五、發明説明（21 ) 例 較 比 同 如 行 進 例器 較應 比反 K水 器脫 容於 1ο 處間 熱柱 加餾 蒸 及後 器然 應。 反序 水程 脫之 7f 於 置 式 方 同 相 之 時 小 每Μ 液 溶 水 酸 硼 達 度 濃 酸 硼 之 器 容 理 處 熱 加 , 於 器係 容理 理處 處熱 熱加 加及 給水 供脫 率， 速pm vr P 份 7 經滴部中央標率局員工消費合作社印製 50托耳減壓，265 °C及50分鐘停留時間條件下進行。得自 加熱處理容器之偏苯三酸之脫水比為99 . 7¾。然後，得自 加熱處理容器之偏苯三酸及偏苯三酸酐混合物連續供給理 論具四階段之蒸餾柱，柱底液K每小時80份速率連續撤出 及循環至加熱處理容器。隨後，又連續撤出3份柱底液。 蒸餾柱係於15托耳減壓下及柱頂溫250 1C及柱底溫2 50-260 °C操作。於穩態下，柱頂與柱底溫差為1 5 °C或Μ下。由蒸 餾柱蒸餾之偏苯三酸酐之純度為99.2¾，熔點為167.5 °C及 熔體色彩A P H A 1 0 0。即使原料具低純度，藉加熱處理可獲 得產物品質改善之偏苯三酸酐。又，因循環利用蒸餾柱底 液，故可克服添加硼酸造成之缺陷及可成功地進行蒸餾毫 無問題。 實例1 5 (第四發明） 加熱處理容器置於比較例5使用之脫水反應器與蒸餾柱 間。於脫水反應器進行如比較例5之相同程序。然後，於 加熱處理容器於50托耳減壓，26 0 1C及1小時停止時間條件 下進行脫水及加熱處理。得自加熱處理容器之偏苯三酸之 脫水比為9 9 . 5 %。然後，於比較例5之相同方式進行脫水。 經蒸餾之偏苯三酸酐純度為99,1¾，熔點為167.4 °C及熔體 色彩為A Ρ Η A 8 0。加熱處理可改良偏苯三酸酐產品純度。 本紙張尺度適用中國國家標準（CNS ) A4規枱（210X 297公i ) Λ , 一 24 一 ^ Μ ' 裝 - ^ 訂 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 577874 A7 五、發明説明（22 ) 比較例8 經由氧化含94%2,4-二甲基苯甲酸，1¾甲基酞酸，U甲 基酞及4¾其它雜質之混合物所得粗偏苯三酸（偏苯三酸含 量96. 1%)M每小時150份之速率連續供給脫水反應器，及 於500托耳，235 °C及停留時間3. 5小時條件下加熱脫水。 得自脫水反應器之偏苯三酸脫水比為92¾。 然後，得自脫水反應器之含偏苯三酸及偏苯三酸酐之混 合物於1 5托耳減壓下連續供給理論上具四階段之蒸餾柱。 蒸餾妥之偏苯三酸酐具有純度為98.6¾，熔點為167.3 °C及 熔體色彩為APHA170。 實例1 6 加熱處理容器置於比較例8使用之脫水反應器與蒸餾柱 間。於脫水反應器進行比較例8之相同程序。然後，於加 熱處理容器，於60托耳減壓，270 °C及停留時間4小時之條 件下進行脫水及加熱處理。得自加熱處理容器之偏苯三酸 脫水比為9 9 , 7 %。 然後，Μ比較例8之相同方式進行蒸餾。由蒸餾柱蒸餾 得之偏苯三酸酐具有純度99.2¾，熔點167.5 °C及熔體色彩 ΑΡΗ A1 00。即使原料具低純度，藉加熱處理獲得產物品質 改良之偏苯三酸酐。 比較例9 加熱處理容器置於比較例8使用之脫水反應器與蒸餾柱 間。於脫水反應器，Μ每小時1 50份速率連續供給如比較 例8使用之相同粗偏苯三酸，及於500托耳，235 1C及停留 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210Χ 297公焓） 0 _ 一 2 5 — (請先閱讀背面之注意事項再填寫本頁)Zr (KOI 0 0. 005 0. 03 0 0 Ce 0 (KOI 0.005 0. 03 0 0 Co 0 0 0 0 0 0.01 Μη 0 * 37 0.37 0. 37 0. 32 0.38 0. 37 Yield (Η! 0 m ΤΜΑ 89. 1 87. 1 89. 8 91.0 80.0 83. 8 Intermediate 3 * 5 7 + 9 4.0 3 * 5 10.4 6 * 7 CEX, = Comparative Example 1 1 Repeat Example 7, but 2, 4- Dimethylbenzaldehyde was replaced by 2,4-dimethylbenzoic acid and supplied at a rate of M 203g / h. The yield of trimellitic acid was 92.0rooU, and the yield of intermediates was 2, 9 m ο 1%. Example 12 Example 7 was repeated, but 2,4-dimethylbenzaldehyde was replaced with 3,4-dimethylbenzaldehyde and supplied at a rate of 182 g / h. The yield of trimellitic acid obtained was 88.1 hi ο 1% and intermediate yield of 2.9 m ο 1 Si; Comparative Example 5 (Third Invention) Obtained by oxidizing 2,4-dimethylbenzaldehyde according to the method described in JP-B-58-22-22 Crude trimellitic acid (trimellitic acid content 97, 5¾) is continuously supplied to the dehydration reactor at a rate of 1.5 parts per hour, and heated and dehydrated at 230 ° C for 3 hours. The trimellitic acid obtained from the dehydration reactor The triacid dehydration ratio is 90¾. Then, the trimellitic acid and the trimellitic acid obtained from the dehydration reactor The mixture of triacid anhydride is applicable to the Chinese National Standard (CNS) Λ4 specification (210X 297 male #) at the size of 1 to 5 paper. I ~ equipment ^ ^ I (Please read the precautions on the back before filling this page) Printed by the Standards Bureau Consumer Cooperatives -21-577874 A7 ΒΊ V. Description of the invention (19) The theoretically two-stage distillation column is continuously supplied under ear pressure, and the bottom liquid is continuously measured at a rate of 3 parts per hour. The distillation column is operated at a column top temperature of 250 ° C and a column bottom temperature of 250 to 260 ° C under a reduced pressure of 15 Torr. At steady state, the temperature difference between the column top and the column bottom is 10 t or less. Distilled trimellitic anhydride The purity is 98.8%, the melting point is 167 + 3 ° C and the melt color is APHA120. The melt color of trimellitic anhydride is melted at 1 90 ° C under atmospheric pressure and compared with the melted trimellitic anhydride and JIS K1557-6.2. Shows the determination of APHA standard solution. Spring example 1 3 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Lithology (read the precautions on the back before filling this page) The heat treatment container was placed in the dehydration reactor and distillation column used in Comparative Example 5. In the dehydration reactor. The procedure of Example 5. Then, the 10¾ boric acid aqueous solution M was supplied to the heat treatment container at a rate of 0.1 parts per hour, and the boron acid concentration of the heat treatment container reached 6 Op pm. Then, dehydration and heat treatment were performed at 50 Torr under reduced pressure, 260 ° C and 10 minutes residence time. The trimellitic acid dehydration ratio obtained from the heat treatment vessel was 99,4¾. Then, the mixture of trimellitic acid and trimellitic anhydride obtained from the heated processing vessel was continuously supplied to a theoretical two-stage distillation column, and the bottom liquid M was continuously withdrawn at a rate of 3 parts per hour. 20 portions are circulated to the heat treatment container. The distillation column is operated at a reduced pressure of 15 Torr at a temperature of 250 ° C at the top of the column and 250 to 260 ° C at the bottom of the column. At steady state, the temperature difference between the top of the column and the bottom of the column is 101C or K. The purity of trimellitic anhydride distilled from a distillation column is 99.2%, the melting point is 167.4 °, and the melt color is ^ 1 ^ 80. Heat treatment can improve the quality of trimellitic anhydride. Comparative Example 6 Contains 94¾ 2, 4-dimethylbenzaldehyde, U methylphthalic acid, and U-methyl paper through oxidation. Applicable to China National Standard (CNS) Λ4 gauge (210X29D > i) 577874 A7 5. Description of the invention ( 2) The crude trimellitic acid (trimellitic acid content 96, U) obtained from a mixture of phthalophthalate and other impurities is continuously supplied to the dehydration reactor at a rate of 150 parts per hour, and at 500 torr, 2 3 Heat dehydration at 5 ° C and 3 + 5 hours residence time. The trimellitic acid dehydration ratio obtained from the dehydration reactor was 92¾. Then, the mixture containing trimellitic acid and trimellitic anhydride obtained from the dehydration reactor was continuously supplied to a theoretically four-stage distillation column under a reduced pressure of 15 Torr, and the bottom liquid was continuously withdrawn at a rate of 3 parts per hour. At steady state, the temperature difference between the top and bottom of the column is 10 ° C or below. Distilled trimellitic anhydride has a purity of 98,6¾, a melting point of 167.3 ° C, and a melt color of APHA170. Comparative Example 7 Printed by the Consumer Cooperative of the Central Bureau of Standards of Yiyi Department (please read the precautions on the back before filling this page). The heat treatment container was placed between the dehydration reactor and distillation column used in Comparative Example 6. The same procedure as in Comparative Example 6 was performed in a dehydration reactor. Then, the 10¾ boric acid aqueous solution K was supplied to the heat treatment container at a rate of 0.4 parts per hour. The boron acid concentration of the heat treatment container reached 267PPII. The dehydration and heat treatment were decompressed at 50 Torr, 2 65 ° C, and the residence time was 50 minutes. Under the conditions. The trimellitic acid dehydration ratio obtained by heat treatment was 99.72. Then, a mixture of trimellitic acid and trimellitic anhydride obtained from the heat-treated container was supplied to a theoretical four-stage distillation column, and the column bottom liquid M was withdrawn at a rate of 3 parts per hour. The distillation column was operated at a reduced pressure of 15 Torr and a column top temperature of 250 ° C. The bottom liquid was concentrated, the temperature at the bottom of the column exceeded 280 ° C, and the temperature difference between the top of the column and the bottom of the column became 30 ° C or more. It is therefore difficult to operate the distillation column. Distilled trimellitic anhydride has a purity of 99.2¾, a melting point of 167.5 ° C, and a melt color of A P H A 1 0 0. Heat treatment can improve the quality of trimellitic anhydride. Example 1 4 This paper size applies the Chinese National Standard (CNS) Λ4 specification (21〇X 297) -2 3 577874 Α7 Β7 V. Description of the invention (21) The comparison of the example is the same as that of the traveling device. The water tank is decapitated in the hot water column for distillation, and the rear tank should respond. Reverse sequence water removal 7f When the set square is in the same phase, the permeate of the water-soluble boron acid solution and the concentrated boron acid solution are heated and heated, and the heat and heat are added and the water supply and removal rate in the container system The speed pm vr P copies 7 were printed at 50 Torr decompression by the Consumer Cooperatives of the Central Standards Bureau of Didi Ministry, under the conditions of 265 ° C and a 50 minute residence time. The dehydration ratio of trimellitic acid obtained from the heat-treated container was 99.72. Then, the trimellitic acid and trimellitic anhydride mixture obtained from the heat treatment vessel were continuously supplied to a theoretical four-stage distillation column, and the bottom liquid K was continuously withdrawn at a rate of 80 parts per hour and recycled to the heat treatment vessel. Subsequently, three consecutive column bottoms were withdrawn. The distillation column is operated at a reduced pressure of 15 Torr and a column top temperature of 250 1C and a column bottom temperature of 2 50-260 ° C. At steady state, the temperature difference between the top and bottom of the column is 15 ° C or M. Trimellitic anhydride distilled from a distillation column has a purity of 99.2¾, a melting point of 167.5 ° C, and a melt color of A P H A 1 0 0. Even if the raw materials have low purity, trimellitic anhydride with improved product quality can be obtained by heat treatment. In addition, since the bottom liquid of the distillation column is recycled, the defects caused by the addition of boric acid can be overcome and the distillation can be successfully performed without any problems. Example 15 (Fourth Invention) A heat treatment vessel was placed between the dehydration reactor and the distillation column used in Comparative Example 5. The same procedure as in Comparative Example 5 was performed in a dehydration reactor. Then, the heat treatment container was decompressed at 50 Torr, and dehydrated and heat-treated under a condition of 2601C and a stop time of 1 hour. The dehydration ratio of trimellitic acid obtained from the heat-treated container was 99.5%. Then, dehydration was performed in the same manner as in Comparative Example 5. Distilled trimellitic anhydride has a purity of 99,1¾, a melting point of 167.4 ° C, and a melt color of A P Η A 80. Heat treatment can improve the purity of trimellitic anhydride products. This paper size applies Chinese National Standard (CNS) A4 gauge (210X 297 male i) Λ, one 24 one ^ Μ 'installed-^ order (Please read the precautions on the back before filling this page) Printed by Industrial and Commercial Cooperatives 577874 A7 V. Description of Invention (22) Comparative Example 8 Crude crude oil obtained by oxidizing a mixture containing 94% of 2,4-dimethylbenzoic acid, 1¾methylphthalic acid, Umethylphthalide and 4¾ other impurities Trimellitic acid (trimellitic acid content of 96.1%) M was continuously supplied to the dehydration reactor at a rate of 150 parts per hour, and heated and dehydrated at 500 Torr, 235 ° C and a residence time of 3.5 hours. The trimellitic acid dehydration ratio obtained from the dehydration reactor was 92¾. Then, the mixture containing trimellitic acid and trimellitic anhydride obtained from the dehydration reactor was continuously fed to a theoretically four-stage distillation column under a reduced pressure of 15 Torr. Distilled trimellitic anhydride has a purity of 98.6¾, a melting point of 167.3 ° C, and a melt color of APHA170. Example 16 A heat-treated container was placed between the dehydration reactor and the distillation column used in Comparative Example 8. The same procedure as in Comparative Example 8 was performed in a dehydration reactor. Then, in a heat treatment container, dehydration and heat treatment were performed under the conditions of reduced pressure of 60 Torr, 270 ° C and a residence time of 4 hours. The trimellitic acid dehydration ratio obtained from the heat-treated container was 99,7%. Then, distillation was performed in the same manner as in Comparative Example 8. Trimellitic anhydride obtained by distillation from a distillation column has a purity of 99.2¾, a melting point of 167.5 ° C, and a melt color of APY A100. Even if the raw material has low purity, trimellitic anhydride with improved product quality can be obtained by heat treatment. Comparative Example 9 A heat treatment vessel was placed between the dehydration reactor and the distillation column used in Comparative Example 8. In the dehydration reactor, M is continuously supplied at the rate of 150 parts per hour as the same crude trimellitic acid as used in Comparative Example 8, and at 500 Torr, 235 1C and stays. 210 × 297 enthalpy) 0 _ One 2 5 — (Please read the precautions on the back before filling this page)
·I ...... n - - - II - I I I I 577874 A 7 B7 五、發明説明（23 ) 時間3. 5小時條件下加熱脫水。於加熱處理容器，於500托 耳減壓，270 °C及停留時間3小時之條件下進行脫水及加熱 處理。得自加熱處理容器之偏苯三酸脫水比為96 , 0¾。 然後，K比較例8之相同方式進行蒸餾。由蒸餾柱蒸餾 得之偏苯三酸酐具有純度98.8%，熔點167.3 °C及熔體色彩 APHA160。可知當加熱處理容器具低度減壓及脫水比低時 ，即使進行加熱處理，偏苯三酸酐之產物品質也未改良。 (請先閱讀背面之注意事項再填寫本頁) 經滴部中央標準局貝工消費合作社印^ 本紙張尺度適用中國國家標準（CNS ) Λ4規梠（210X 297公# ) _ 〇6 -· ...... n---II-I I I I 577874 A 7 B7 V. Description of the invention (23) Time 3.5 hours under the conditions of heating and dehydration. Dehydration and heat treatment were performed in a heat-treated container under the conditions of reduced pressure of 500 Torr, 270 ° C and a residence time of 3 hours. The trimellitic acid dehydration ratio obtained from the heat-treated container was 96,0¾. Then, K was distilled in the same manner as in Comparative Example 8. Trimellitic anhydride distilled from a distillation column has a purity of 98.8%, a melting point of 167.3 ° C, and a melt color of APHA160. It can be known that when the heat treatment container has a low degree of decompression and a low dehydration ratio, the product quality of trimellitic anhydride is not improved even if heat treatment is performed. (Please read the precautions on the reverse side before filling out this page) Printed by the Shell Department Consumer Cooperatives of the Central Bureau of Standards of the Ministry of ^ This paper size applies Chinese National Standard (CNS) Λ4 Regulations (210X 297 公 #) _ 〇6-